Sulfur compounds

ABSTRACT

Sulfur compounds of the formula ##STR1## where n is 0 or 2, 
     R 1  and R 2  are hydrogen, C 1  -C 6  -alkyl, C 1  -C 6  -alkoxy, halogen, nitro, amino, hydroxysulfonyl, C 1  -C 6  -alkoxycarbonyl or unsubstituted or substituted carbamoyl, 
     A is methylene, sulfonyl or a radical of the formula CH 2  --CO or CH 2  --SO 2 , 
     X is a direct bond or unsubstituted or substituted C 1  -C 8  -alkylene and 
     Y is vinyl or a radical of the formula C 2  H 4  Q, where Q is hydroxyl or a group which can be removed under alkaline reaction conditions, 
     and a process for their preparation are described.

This is a Continuation of application Ser. No. 08/423,849 filed on Apr. 18, 1995, now U.S. Pat. No. 5,491,232.

The present invention relates to novel sulfur compounds of the formula I ##STR2## where n is 0 or 2,

R¹ and R² independently of one another in each case are hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen, nitro, amino, hydroxysulfonyl, C₁ -C₆ -alkoxycarbonyl, carbamoyl or C₁ -C₆ -mono- or dialkylcarbamoyl,

A is methylene, carbonyl, sulfonyl or a radical of the formula CH₂ --CO or CH₂ --SO₂, the methylene group in each case being linked to the benzene ring,

X is a direct bond, C₁ -C₈ -alkylene which may be interrupted by 1 to 3 oxygen atoms in ether linkage, 1 to 3 imino groups or 1 to 3 C₁ -C₄ -alkylimino groups, or a radical of the formula L¹ --CO--NR³ --L², where L¹ and L² independently of one another in each case are C₁ -C₄ -alkylene and R³ is hydrogen, C₁ -C₄ -alkyl or phenyl, and

Y is vinyl or a radical of the formula C₂ H₄ Q, where Q is hydroxyl or a group which can be removed under alkaline reaction conditions,

and a process for their preparation.

It is an object of the present invention to provide novel sulfur compounds which have a benzamide structural moiety. The novel substances are intended to be advantageously suitable for the preparation of dyestuffs.

We have now found that this object is achieved by the sulfur compounds of the formula I characterized in greater detail at the outset.

All alkyl and alkylene groups occurring in the abovementioned formula can be either straight-chain or branched.

R¹, R² and R³ are eg. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

R¹ and R² are furthermore eg. pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2-methylpentyloxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, tert-pentyloxycarbonyl, hexyloxycarbonyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl, mono- or dipentylcarbamoyl, mono- or dihexylcarbamoyl or N-methyl-N-ethylcarbamoyl.

X, L¹ and L² are eg. CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, CH(CH₃)CH₂ or CH(CH₃)CH(CH₃).

X is furthermore eg. (CH₂)₅, (CH₂)₆, (CH₂)₇, (CH₂)₈, C₂ H₄ --O--C₂ H₄, C₂ H₄ --NH--C₂ H₄, C₂ H₄ --N(CH₃)--C₂ H₄, C₂ H₄ --O--C₂ H₄ --O--C₂ H₄, C₂ H₄ --NH--C₂ H₄ --NH--C₂ H₄, C₂ H₄ --N (CH₃)--C₂ H₄ --N(CH₃)--C₂ H₄, C₂ H₄ --O--C₂ H₄ --N (CH₃)--C₂ H₄, C₂ H₄ --O--C₂ H₄ --O--C₂ H₄, C₂ H₄ --NH--C₂ H₄ --NH--C₂ H₄ --NH--C₂ H₄, C₂ H₄ N (CH₃)--C₂ H₄ --N (CH₃)--C₂ H₄ --N (CH₃)--C₂ H₄, C₂ H₄ --CO--NH--C₂ H₄, C₂ H₄ CO--N (CH₃)--C₂ H₄, C₃ H₆ --CO--NH--C₂ H₄, C₂ H₄ --CO--NH--C₃ H₆, C₃ H₆ --CO--NH--C₃ H₆ or C₃ H₆ --CO--N(CH₃)--C₃ H₆.

Q is hydroxyl or a group which can be removed under alkaline reaction conditions. Such groups are eg. chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, OSO₃ H, SSO₃ H, OP(O)(OH)₂, C₁ -C₄ -alkylsulfonyloxy, phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -dialkylamino or a radical of the formula ##STR3## where Z¹, Z² and Z³ are identical or different and independently of one another in each case have the meaning of C₁ -C₄ -alkyl or benzyl and An.sup.⊖ in each case has the meaning of an equivalent of an anion. Suitable anions here are eg. fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methanesulfonate, benzenesulfonate or 2- or 4-toluenesulfonate.

Preferred sulfur compounds of the formula I are those where A is methylene, carbonyl or the radical of the formula CH₂ --CO.

Preferred sulfur compounds of the formula I are furthermore those where X is C₁ -C₈ -alkylene which may be interrupted by 1 to 3 oxygen atoms in ether linkage.

Preferred sulfur compounds of the formula I are furthermore those where R¹ is hydrogen or amino and R² is hydrogen.

Preferred sulfur compounds of the formula I are furthermore those where n is 2.

Particularly preferred sulfur compounds of the formula I are those where A is methylene.

Particularly preferred sulfur compounds of the formula I are furthermore those where R¹ is amino and R² is hydrogen.

The novel sulfur compounds of the formula I can be obtained in a manner known per se. For example, a benzene derivative of the formula II ##STR4## where R¹, R² and A in each case have the abovementioned meanings, can be reacted with an amine of the formula III

    H.sub.2 N--X--S(O).sub.n --Y                               (III),

where n, X and Y in each case have the abovementioned meanings.

An advantageous procedure is the reaction of the benzene derivatives of the formula II first with a thioether of the formula IIIa

    H.sub.2 N--X--S--Y                                         (IIIa),

where X and Y in each case have the abovementioned meanings, and subsequent oxidation of the sulfide to the sulfonyl group, eg. using hydrogen peroxide.

R¹ and R², if they are different from hydrogen, can also be subsequently introduced into the benzene ring by a route known per se. In particular when introducing the hydroxysulfonyl group or the nitro group, which can then be reduced to the amino group, this route is preferred.

The novel sulfur compounds of the formula I are useful intermediates for the preparation of dyestuffs, in particular of reactive dyestuffs.

The following examples are intended to illustrate the invention in greater detail.

EXAMPLE

A mixture of 302 g of 2-aminoethyl-2'-hydroxyethyl sulfide and 268 g of phthalide was heated at from 220° to 225° C. for 3 h. After cooling, 250 ml of water were added and the pH was adjusted to 6.5 using sulfuric acid. After addition of 1 g of tungstic acid, 680 g of 30% strength by weight aqueous hydrogen peroxide solution were added dropwise at from 65° to 80° C. in the course of 1 h. After cooling, the precipitate was filtered off with suction and dried. 407 g of the compound of the formula ##STR5## were isolated.

M.p.: 172° to 174° C.

NMR (D₆ -DMSO): 3.31 (m, 2), 3.52 (m, 2), 3.81 (m, 2), 4.00 (m, 2), 4.55 (s, 2), 5.20 (t,1), 7.5-7.7 (m, 4).

EXAMPLE 2

174 g of the compound from Example 1 were introduced with cooling into 600 g of 96% strength by weight sulfuric acid and the mixture was stirred at room temperature for 8 h. After cooling to from 0° to 5° C., 34.7 g of 100% strength by weight nitric acid in 70 g of 96% strength by weight sulfuric acid were added in the course of 3 h. After a further 3 h, the mixture was diluted with ice, the pH was adjusted to 0.2 to 0.3 using solid sodium hydrogen carbonate and the precipitate was filtered off with suction. 240 g of the compound of the formula ##STR6## were isolated in the form of a moist press cake.

M.p.: 154° to 157° C. (from butanol).

EXAMPLE 3

240 g of the moist press cake from Example 2 were dissolved in 700 ml of water, the pH was adjusted to 4.5 using sodium acetate and hydrogen gas was introduced at from 50° to 55° C. in the presence of 5 g of a palladium catalyst. After absorption of hydrogen was complete, the catalyst was filtered off and the filtrate concentrated under reduced pressure. 177 g of a compound of the formula ##STR7## were isolated after drying.

Content determination by diazotization: 69%.

NMR (D₆ -DMSO): 3.50 (m, 4), 3.92 (m, 2), 4.12 (m, 2), 4.38 (s, 2), 5.30 (s, 2), 6.8 (m, 2), 7.2 (d, 1)

EXAMPLE 4

A solution of 69 g of the compound from Example 3 in 500 ml of water was adjusted to a pH of 10 at from 25° to 30° C. using sodium carbonate. An oil deposited which slowly crystallized. The crystals were filtered off with suction and after drying 42 g of the compound ##STR8## were isolated.

M.p.: 144° to 148° C.

NMR (D₆ -DMSO): 3.55 (m, 2), 3.88 (m, 2), 4.35 (s, 2), 5.38 (s, 2), 6.3 (m, 2), 6.85 (m, 2), 7.02 (m, 1), 7.21 (d, 1)

EXAMPLE 5

135 g of the compound from Example 1 were stirred in 500 g of xylene and treated slowly with 119 g of thionyl chloride at from 65° to 68° C. After a further 3 h at from 65° to 68° C., the mixture was cooled and the precipitate was filtered off with suction. After drying, 144 g of the compound of the formula ##STR9## were isolated.

M.p.: 162° to 164° C.

The procedure was then as described in Examples 2 and 3 and the compound of the formula ##STR10## was obtained.

M.p.: 169° to 171° C.

EXAMPLE 6

The procedure was as described in Example 1, but the phthalide was replaced by 296 g of phthalic anhydride. 410 g of the compound of the formula ##STR11## were obtained.

M.p.: 126° to 130° C.

The procedure was then as described in Examples 2 and 3 and the compound of the formula ##STR12## was obtained.

NMR (D₆ -DMSO): 3.45 (m, 4), 3.95 (t, 2), 4.10 (t, 2), 6.5 (s, 2), 6.80 (dd, 1), 6.95 (s, 1), 7.50 (d, 1)

EXAMPLE 7

The compound from Example 6 was reacted in a similar manner to Example 4. The compound of the formula ##STR13## was thus obtained.

M.p.: 143° to 145° C.

EXAMPLE 8

Homophthalic anhydride was reacted with 2-aminoethyl-2'-hydroxyethyl sulfide as described in Example 1 and the oil obtained was oxidized using 30% strength by weight aqueous hydrogen peroxide. The compound of the formula ##STR14## was thus isolated.

M.p.: 146° to 149° C.

NMR (D₆ -DMSO): 3.4 (m, 4), 3.80 (m, 2), 4.15 (s, 2), 4.30 (m, 2), 5.21 (t, 1), 7.41 (m, 1), 7.50 (m, 1), 7.68 (m, 1), 8.08 (m, 1) 

We claim:
 1. A sulfur compound of the formula I ##STR15## where n is 0 or 2,R¹ and R² independently of one another in each case are hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen, nitro, amino, hydroxysulfonyl, C₁ -C₆ -alkoxycarbonyl, carbamoyl or C₁ -C₆ -mono- or dialkylcarbamoyl, A is methylene, sulfonyl or a radical of the formula CH₂ --CO or CH₂ --SO₂, the methylene group in each case being linked to the benzene ring, X is a direct bond, C₁ -C₈ -alkylene which may be interrupted by 1 to 3 oxygen atoms in ether linkage, 1 to 3 imino groups or 1 to 3 C₁ -C₄ -alkylimino groups, or a radical of the formula L¹ --CO--NR³ --L², where L¹ and L² independently of one another in each case are C₁ -C₄ -alkylene and R³ is hydrogen, C₁ -C₄ -alkyl or phenyl, and Y is vinyl or a radical of the formula C₂ H₄ Q, where Q is hydroxyl or a group which can be removed under alkaline reaction conditions.
 2. A sulfur compound as claimed in claim 1, wherein A is methylene, or the radical of the formula CH₂ --CO.
 3. A sulfur compound as claimed in claim 1, wherein X is C₁ -C₈ -alkylene which may be interrupted by 1 to 3 oxygen atoms in ether linkage.
 4. A sulfur compound as claimed in claim 1, wherein R¹ is hydrogen or amino and R² is hydrogen. 